Preparation of polysaccharide betainate type compounds, compounds obtained, their use and compositions comprising them

ABSTRACT

A process for preparing compounds from the polysaccharide betainate family, novel compounds so obtained, and their use in. cosmetics or in dermatology, as well as the compositions, such as cosmetic or dermatological compositions, comprising said novel compounds.

Disclosed herein are methods for preparing compounds from thepolysaccharide betainate family, novel compounds so obtained, and theiruse in cosmetics or in dermatology, as well as novel compositions, suchas cosmetic or dermatological compositions, comprising said novelcompounds.

Certain starch betainates and their derivatives are compounds wellknown, for example, in the field of paper-manufacturing. It is known,such as from International Patent Application WO-A-00/15669 and thearticle “Preparation of starch betainate: a novel cationic starchderivative” in 41 Carbohydrate Polymers 277-283 (2000), that potatostarch betainates can be synthesized by esterifying hydroxyl groups inthe starch with a betainyl chloride. Esterification is carried out inpyridine and 1,4-dioxane at a temperature of about 110° C.

But that synthesis can be difficult to carry out, due to the operatingconditions and to the unstable nature of the betaine derivativesemployed, which can impair the reaction yield. After a great deal ofresearch, the inventors have developed at least two novel processes forsynthesizing starch betainates, which can produce such compounds muchmore easily in an improved yield. Further, said processes can allownovel compounds from the polysaccharide betainate family to be prepared.These compounds can have at least one property that can be exploited inthe cosmetic or dermatological fields.

In one embodiment, a process for preparing compounds of formula (I) aswill be defined below is disclosed. In the process, a polysaccharide isreacted with an N,N-dialkylaminocarboxylic acid of formula (II) as willbe defined below, in the presence of at least one reaction activator.Then the ester formed is quaterinized using a quaternization agent.

In another embodiment, another process for preparing compounds offormula (I) as will be defined below is disclosed. In the process, apolysaccharide is reacted with a salt of anN,N,N-trialkylammoniocarboxylic acid of formula (III) as will be definedbelow. This reaction is carried out in a polar aprotic solvent and takesplace in the presence of at least one reaction activator.

Further disclosed herein is a compound of formula (I) as will be definedbelow, excluding compounds of formula (I) in which Y represents apolymeric starch structure, A represents —CH₂—, and R1=R2=R3=—CH₃.

Further disclosed herein is a composition, such as a cosmetic and/ordermatological composition, comprising at least one compound as definedabove in a cosmetically or dermatologically acceptable medium.

Even further disclosed herein is a process for cosmetic treatment of akeratinous support chosen from skin, scalp, hair, eyelashes, eyebrows,nails, and mucous membranes, comprising applying to said keratinoussupport a composition as defined above.

In one embodiment, the compounds disclosed herein are compounds from thepolysaccharide betainate family of formula (I):

in which:

-   R₁, R₂, and R₃, which may be identical or different, are chosen from    linear and branched, saturated and unsaturated C₁-C₃₀ hydrocarbon    radicals optionally interrupted by at least one heteroatom chosen    from N, O, and S and optionally substituted with at least one entity    chosen from —OH, halogen atoms (such as chlorine, bromine and    iodine) and C₆-C₂₂ aryl radicals;-   A is chosen from linear and branched, saturated and unsaturated    divalent C₁-C₂₂ hydrocarbon radicals, optionally interrupted by at    least one hetero atom chosen from N, O, and S and optionally    substituted with at least one hydroxyl radical;-   X⁻ is an anion derived from an acid chosen from mineral and organic    acids; and-   Y is a polysaccharide residue;    excluding compounds of formula (I) in which Y represents a polymeric    starch structure, A is —CH₂—, and R1=R2=R3=—CH₃.

For example, R1, R2, and R3, which may be identical or different, arechosen from linear and branched, saturated C₁-C₁₄ hydrocarbon radicals,such as C₂-C₁₂ radicals, further such as a methyl radical.

In one embodiment, R1, R2, and R3 are identical and can, for example, bechosen from linear and branched saturated C₁-C₁₄ hydrocarbon radicals,such as a methyl radical.

In another embodiment, A is chosen from linear and branched saturateddivalent C₁-C₄ hydrocarbon radicals, such as methylene, ethylene,propylene and butylene, and further such as methylene.

Anions derived from an organic acid include, but are not limited to,citrates, lactates, and tartrates. Anions derived from a mineral acidinclude, but are not limited to, chlorides, bromides, iodides, andsulphates. For example, said anions are chlorides.

The polysaccharides can be chosen from natural and modifiedpolysaccharides. Natural polysaccharides include starches, e.g.,starches from vegetable origins such as maize, potato, oats, rice,tapioca, sorghum, barley and wheat; polysaccharides from seed gums suchas guar, tara, carob, psyllium, linseed, okra, tamarind, quince gums;polysaccharides from microbial gums such as curdlan, pullulan, dextran,grifolan, schizophyllan, spirulinan, krestin, xanthan, scleroglucan,gellan, succinoglycan gums; polyfructoses such as inulin and levan;algae extracts (agar, alginate, caragheenans, fucoidane, furcellerane,laminarane); extracts from plant exudates (gum arabic, ghatti gum,karaya gum, adraganth gum); celluloses; and chitins.

Modified polysaccharides means polymers obtained by hydrolysis,esterification, etherification, amidation, oxidation, reduction,modification of the hydroxyl groups, covalent incorporation oforganometallic residues, grafting, N-acylation, N-alkylation,deamination, or any other modification of the nitrogen-containingfunctions of polysaccharides containing said functions and/orhalogenation using processes known in the art.

Examples of appropriate processes include:

-   (a) partial hydrolysis of polysaccharide chains using enzymatic    treatment, heat treatment, acid treatment or oxidizing treatment;-   (b) partial or complete hydrolysis of naturally present ester    functions;-   (c) partial or complete esterification and/or amidation of naturally    present carboxylic functions;-   (d) carboxylation using, for example, monochloroacetate;-   (e) oxidation of hydroxyl functions in the polysaccharide;-   (f) polyoxyalkylenation;-   (g) hydrophobic modification of a polysaccharide, for example by    reacting a C₁-C₂₂ alkylating agent such as methyl chloride or nonyl    chloride on alkali cellulose or on hydroxyethyl cellulose;-   (h) crosslinking of polysaccharide chains; and-   (i) grafting, for example, resulting in introducing into the    molecule moieties such as polydimethylsiloxane, polyacrylic acid or    polymethacrylic acid, polyacrylamide, polymethacrylamide,    polyacrylonitrile, sodium polystyrene sulphonate,    polyvinylpyrrolidone, polyhydroxyalkyl(meth)acrylate, or the sodium    salt of poly(2-acrylamido-2-methylpropanesulphonic) acid.

Modified polysaccharides include hydroxyalkyl celluloses, such ashydroxyethyl celluloses, hydroxyalkyl guars such as hydroxypropyl guar,carboxyalkyl celluloses, carboxyalkyl starches, modified and unmodifiedchitosans, maltodextrins and cyclodextrins.

The novel compounds can be prepared using one of the following processesas disclosed herein.

In one embodiment, a preparation process (“the first preparationprocess”) is disclosed, comprising:

-   -   (i) reacting a polysaccharide with an N,N-dialkylaminocarboxylic        acid of formula (II):

in the presence of at least one reaction activator; and (ii) quatemizingthe ester formed using a quatemization agent to fix the radical R₂ tothe nitrogen atom.

In accordance with this process, in (i), a polysaccharide(N,N-dialkylamino)ester is formed. Quartemization of this ester resultsin the production of the polysaccharide N,N,N-trialkylaminoester salt in(ii).

In one embodiment, the reaction between the polysaccharide and the acidis carried out in a suitable solvent.

In another embodiment, the polysaccharide and theN,N-dialkylaminocarboxylic acid are dissolved or dispersed in saidsuitable solvent prior to said reaction.

Further in another embodiment, the polysaccharide and theN,N-dialkylaminocarboxylic acid are dissolved or dispersed in saidsuitable solvent prior to adding the reaction activator

The solvent is, for example, polar and aprotic. The solvent can, forexample, be chosen from at least one of dimethylsulphoxide (DMSO) anddimethylformamide.

The reaction activator can, for example, be chosen from carbodiimidessuch as N,N′-diisopropylcarbodiimide; hydroxybenzotriazole,4-dimethylaminopyridine, and mixtures thereof.

Also, the reaction is, for example, carried out at ambient temperature.

The quaternization agent used can be any quaternization agent known tothe skilled person. This agent can, for example, be a halide such as achloride, an iodide and a bromide, such as a C₁-C₃₀ alkyl halide, and asulphate, such as a C₁-C₃₀ alkyl sulphate. In one embodiment, thequatemization agent is chosen from methyl iodide (Mel) and methylsulphate (Me₂SO₄).

Quaternization is, for example, carried out at a temperature rangingfrom about 20° C. to about 70° C., such as from about 22° C. to about27° C.

Quaternization can be carried out with an isolated compound and/or inanother solvent medium that differs from the reaction solvent.

Another preparation process (“the second preparation process”) comprisesreacting a polysaccharide with a salt of anN,N,N-trialkylammoniocarboxylic acid of formula (III):

wherein the reaction is carried out in a polar aprotic solvent; and thereaction takes place in the presence of at least one reaction activator.

In one embodiment, the polysaccharide and the acid salt are dissolved ordispersed in the polar aprotic solvent prior to the reaction.

The polar aprotic solvent is, for example, chosen fromdimethylsulphoxide (DMSO) and dimethylformamide.

In another embodiment, the polysaccharide and the acid salt aredissolved or dispersed in the solvent prior to adding the reactionactivator.

The reaction activator is, for example, chosen from carbodiimides suchas N,N′-diisopropylcarbodiimide; hydroxybenzotriazole,4-dimethylaminopyridine, and mixtures thereof.

This reaction is, for example, carried out at ambient temperature. Thisreaction is carried out for a period of time, such as from about 3 to 24hours.

Polysaccharides that can be used in one of those processes are similarto those described above.

Examples of N,N-dialkylaminocarboxylic acids that can be used in thefirst preparation process include N,N-dimethylglycine (orN,N-dimethylaminoacetic acid), N,N-dimethyl-β-aminopropanoic acid,N,N-dimethyl-γ-aminobutanoic acid, N,N-dimethyl-5-aminopentanoic acidand N,N-dimethylbenzylaminocarboxylic acid. For example, theN,N-dialkylaminocarboxylic acid is N,N-dimethylglycine.

Examples of N,N,N-trialkylammoniocarboxylic acid salts that can be usedin the second preparation process include salts ofN,N,N-trimethylammonioacetic acid (or N,N,N-trimethylglycine),N,N,N-trimethyl-β-ammoniopropanoic acid,N,N,N-trimethyl-γ-ammoniobutanoic acid,N,N,N-trimethyl-5-ammoniopentanoic acid, andN,N,N-trimethylbenzylammoniocarboxylic acid.

These salts can be derived from an acid chosen from organic acids, forexample, citrates, lactates and tartrates, and mineral acids, such ashalides (e.g., chlorides, bromides, iodides), and sulphates. In oneembodiment, said salts are chlorides. The chloride ofN,N,N-trimethylammonioacetic acid, also known as betainyl chloride, canalso be used.

The two preparation processes described above can further comprise atleast one subsequent option, such as anion exchange or purification, forexample, ultrafiltration.

The novel compounds disclosed herein can be present in the cosmetic ordermatological compositions in a concentration ranging, for example,from about 0.01% to about 20% by weight relative to the total weight ofthe composition, such as from about 0.05% to about 15% by weight, andfurther such as from about 0.1% to about 10% by weight relative to thetotal weight of the composition.

The cosmetic or dermatological compositions disclosed herein comprise acosmetically or dermatologically acceptable medium, i.e., a medium thatis compatible with application to a keratinous substance such as skin,scalp, mucous membranes, nails, eyelashes, eyebrows, body, head hair orany other cutaneous zone of face or body.

The pH of said composition is ranging, for example, from about 1 toabout 13, such as from about 2 to about 12.

The cosmetically or dermatologically acceptable medium can comprisewater and/or at least one organic solvent chosen from cosmetically anddermatologically acceptable organic solvents. The at least one organicsolvent can be in an amount ranging from about 1% to about 98% by weightrelative to the total weight of the composition. The at least oneorganic solvent can be chosen from hydrophilic organic solvents,lipophilic organic solvents, and amphiphilic organic solvents.

Hydrophilic organic solvents that can be used are chosen, for example,from linear and branched monoalcohols comprising from 1 to 8 carbonatoms, such as ethanol, propanol, butanol, isopropanol and isobutanol;polyethylene glycols comprising from about 6 to about 80 mol of ethyleneoxide; polyols such as propylene glycol, butylene glycol, glycerol andsorbitol; mono- and dialkyl isosorbide with alkyl groups that comprisefrom 1 to 5 carbon atoms such as dimethyl isosorbide; glycol ethers suchas diethylene glycol monomethyl ether and diethylene glycol monoethylether; and propylene glycol ethers such as dipropylene glycol methylether.

Lipophilic organic solvents that can be used include liquid fatty esterssuch as diisopropyl adipate, dioctyl adipate, and alkyl benzoates.

Amphiphilic organic solvents that can be used include polyols such asderivatives of polypropylene glycol (PPG), for example, esters ofpolypropylene glycol and fatty acids, and esters of PPG and fattyalcohols such as PPG-23 oleyl ether and PPG-36 oleate.

The compositions can further comprise at least one complementarycompound chosen from monosaccharides, oligosaccharides andpolysaccharides, which may or may not be hydrolysed, and which may bemodified or unmodified, identical or not identical, and different fromthe novel compounds disclosed herein. Such compounds can, for example,be chosen from those described in the “Encyclopaedia of Polymer Scienceand Engineering,” vol. 13, pp. 87-162 and vol. 12, pp. 658-690, JohnWiley & Sons, 2d ed., 1988, and in “Polymers in Nature,” by E. A.MacGregor & C. T. Greenwood, John Wiley & Sons, Chapter 6, pp.240-328,1980, and in “Industrial Gums—Polysaccharides and theirDerivatives,” edited by Roy L. Whistler (Academic Press Inc., 2d ed.).

These compounds include, but are not limited to, glucanes such asβ-glucanes; modified or unmodified starches, such as those from cereals,for example wheat, maize and rice, from vegetables such as white peas,from tubers such as potatoes and cassava; amylase, amylopectin,glycogen, dextrans; celluloses and their derivatives such as methylcelluloses, hydroxyalkyl celluloses, ethylhydroxyethyl celluloses,carboxymethyl celluloses, fructosans, inulin, levan, mannans, xylans,lignins, arabans, galactans, galacturonans; chitin, chitosans andderivatives thereof; glucoronoxylans, arabinoxylans, xyloglucans;glucomannans; pectic acids and pectins; alginic acid and alginates;arabinogalactans, carragheenans, agars, glycosaminoglucans, gum arabics,tragacanth gums, ghatti gums, karaya gums, carob gums, xanthan gums,cyclodextrins, and mixtures thereof.

The novel compositions can also comprise at least one complementarycompound chosen from amino acids, oligopeptides, peptides and proteins,which may or may not be hydrolysed, and which may be modified orunmodified. These amino acids can include, for example, cysteine,lysine, alanine, N-phenylalanine, arginine, glycine, leucine, andmixtures thereof. Examples of oligopeptides, peptides or proteins, whichmay or may not be hydrolysed, and which may be modified or unmodifiedinclude modified or unmodified hydrolysates or wool or silk proteins,and vegetable proteins such as wheat proteins.

The novel compositions can comprise at least one complementary compoundchosen from branched and unbranched fatty alcohols and acids. Suitablefatty acids include, for example, C₈-C₃₀ carboxylic acids such aspalmitic acid, oleic acid, linoleic acid, myristic acid, stearic acid,lauric acid, and mixtures thereof. Suitable fatty alcohols include, forexample, C₈-C₃₀ alcohols such as palmitylic alcohol, oleic alcohol,linoleyl alcohol, myristyl alcohol, stearyl alcohol, lauryl alcohol, andmixtures thereof.

Also, the novel compositions can comprise at least one complementarycompound chosen from waxes of animal, vegetable, and mineral origin. Asused herein, the term “wax” means a lipophilic compound that is a solidat ambient temperature (about 25° C.), with a reversible solid/liquidchange of state and with a melting point of more than about 40° C. andup to about 200° C., and having an anisotropic crystalline organizationin the solid state. In general, the size of the wax crystals is suchthat the crystals diffract and/or diffuse light, endowing thecomposition comprising it with a cloudy, more or less opaque appearance.Heating the wax to its melting point renders it miscible with oils tofonm a microscopically homogeneous mixture, but cooling the temperatureof the mixture to ambient temperature causes the wax to recrystallize inthe oils of the mixture, which is detected microscopically andmacroscopically (opalescence).

Suitable waxes include waxes of animal origin such as beeswax,spermaceti, lanolin wax, and lanolin derivatives; waxes of vegetableorigin such as carnauba wax, candelilla wax, ouricury wax, Japan wax,cocoa butter or waxes from cork fibres and sugarcane; and waxes ofmineral origin such as paraffin waxes, vaseline waxes, lignite waxes,microcrystalline waxes, ozokerites, and mixtures thereof.

The compositions can also comprise at least one complementary compoundchosen from ceramides and pseudo-ceramides. Examples include ceramidesin classes I, II, III, and IV according to DOWNING's classification, andmixtures thereof, such as N-oleyidehydrosphingosin.

The compositions can comprise at least one hydroxylated organic acidchosen from acids that are well known and used in the art. For example,citric acid, lactic acid, tartaric acid, malic acid, and mixturesthereof may be used.

Moreover, the compositions can comprise at least one sunscreen chosenfrom UV-A and UV-B active sunscreens that are known to the skilledperson. Examples include dibenzoylmethane derivatives such as4-methyidibenzoylmethane, 4-isopropyldibenzoylmethane,4-tert-butyldibenzoylmethane, 2,4-dimethyidibenzoylmethane,4-tert-butyl-4′-diisopropyldibenzoylmethane, para-aminobenzoic acid andits esters such as 2-ethylhexyl para-dimethylaminobenzoate andethyl-N-propyloxylated para-aminobenzoate, salicylates such astriethanolamine salicylate, cinnamic acid esters such as 2-ethylhexyl4-methoxycinnamate, methyl diisopropylcinnamate, methyl anthranilate,benzotriazole derivatives, triazine derivatives, β,β′-diphenylacrylatederivatives such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and ethyl2-cyano-3,3-diphenylacrylate, 2-phenylbenzimidazole-5-sulphonic acid andits salts, benzophenone derivatives, benzylidenecamphor derivatives,silicone filters, and mixtures thereof.

Additionally, compositions can comprise at least one complementarycompound chosen from antioxidants and free radical scavengers. Examplesinclude ascorbic acid, ascorbyl compounds such as ascorbyl dipalmitate,t-butylhydroquinone, polyphenols such as phloroglucinol, sodiumsulphite, erythorbic acid, flavonoids, and mixtures thereof.

The compositions can also comprise at least one chelating agent chosenfrom EDTA (ethylenediaminetetraacetic acid) and its salts, such asdisodium EDTA and dipotassium EDTA, phosphated compounds such as sodiummetaphosphate, sodium hexametaphosphate, tetrapotassium pyrophosphate,phosphonic acids and their salts such as salts ofethylenediaminetetramethylenephosphonic acid, and mixtures thereof.

The compositions can further comprise at least one complementarycompound chosen from antifungal and antibacterial agents chosen from thefollowing examples:

-   (a) benzethonium chloride, benzalkonium chloride, chlorhexidine,    chloramine T, chloramine B, 1,3-dibromo-5,5-dimethylhydantoin,    1,3-dichloro-5,5-dimethylhydantoin,    3-bromo-1-chloro-5,5-dimethylhydantoin and N-chlorosuccinimide;-   (b) 1-hydroxy-2-pyridone derivatives such as    1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone and    1-hydroxy-4,6-dimethyl-2-pyridone;-   (c) trihalogenocarbamides;-   (d) triclosan;-   (e) azole compounds such as climbazole, ketoconazole, clotrinazole,    econazole, isoconazole and miconazole b;-   (f) antifungal polymers such as amphotericin B and nystatin;-   (g) selenium sulphides;-   (h) sulphur in its different forms, cadmium sulphide, allantoin,    coal tar and wood tar and their derivatives, such as cade oil,    undecylenic acid, fumaric acid, and allylamines such as terbinafine;-   (i) and a mixture thereof.

It is also possible to use those agents in the form of thephysiologically acceptable acid addition salts thereof, such as in theform of salts of sulphuric acid, nitric acid, thiocyanic acid,hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid,acetic acid, benzoic acid, glycolic acid, aceturic acid, succinic acid,nicotinic acid, tartaric acid, maleic acid, palmitic acid,methanesulphonic acid, propanoic acid, 2-oxopropanoic acid, propanedioicacid, 2-hydroxy-1,4-butanedioic acid, 3-phenyl-2-propenoic acid,hydroxybenzeneacetic acid, ethanesulphonic acid,2-hydroxyethanesulphonic acid, 4-methylbenzenesulphonic acid,4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid, 2-acetyloxybenzoicacid, picric acid, lactic acid, citric acid, malic acid, oxalic acid,and amino acids.

The antifungal or antibacterial acids mentioned above can also be usedin the form of their addition salts of physiologically acceptableorganic or inorganic bases. Examples of the organic bases includealkanolamines with low molecular weights such as ethanolamine,diethanolamine, N-ethylethanolamine, triethanolamine,diethylaminoethanol, 2-amino-2-methylpropanedione; non-volatile basessuch as ethylenediamine, hexamethylenediamine, cyclohexylamine,benzylamine, N-methylpiperazine; quatemary ammonium hydroxides, forexample trimethylbenzyl hydroxide; and guanidine and its derivatives, inparticular alkyl derivatives. Examples of the inorganic bases includesalts of alkali metals such as sodium and potassium; ammonium salts,salts of alkaline-earth metals such as magnesium and calcium; and saltsof di-, tri- or tetra-valent cationic metals such as zinc, aluminium andzirconium. Alkanolamines, ethylenediamine and inorganic bases such asalkali metal salts can, for example, be used.

The compositions can additionally comprise at least onedandruff-regulating agent such as succinylchitosan and poly-palanine,and mixtures thereof.

The compositions can further comprise at least one thickening agent suchas azulene or glycyrrhetinic acid, and mixtures thereof.

Additionally, the compositions can comprise at least one polymer chosenfrom cationic polymers. Cationic polymer means any polymer chosen frompolymers containing at least one cationic group and polymers containingat least one group that is ionizable to a cationic group. Suitablecationic polymers for use can be chosen from any of those that are knownto improve the cosmetic properties of hair treated with detergentcompositions, such as those described in European patent applicationEP-A-0 337 354 and in French Patent Applications FR-A-2 270 846, FR-A-2383 660, FR-A-2 598 611, FR-A-2 470 596, and FR-A-2 519 863. Examples ofthe cationic polymers include those containing moieties comprising atleast one amine group chosen from primary, secondary tertiary andquatemary amine groups, which can either form part of the main polymerchain or be carried by a side substituent bonded directly to the mainpolymer chain.

The cationic polymers used generally have a number average molecularmass in the range from about 500 to about 5×10⁶, such as in the rangefrom about 10³ to about 3×10⁶. These cationic polymers include polymersof the polyamine, polyaminoamide, and quaternary polyammonium type, suchas those described in French Patents FR-A-2 505 348 and FR-A-2 542 997.The described cationic polymers are chosen, for example, from:

-   (1) homopolymers and copolymers derived from acrylic acid or    methacrylic acid esters or amides;-   (2) cellulose ether derivatives comprising quaternary ammonium    groups described in French Patent FR-A-1 492 597;-   (3) cationic cellulose derivatives such as cellulose copolymers or    cellulose derivatives grafted with a hydrosoluble quaternary    armmonium monomer and as is described in U.S. Pat. No. 4,131,576,    such as hydroxyalkyl celluloses, for example hydroxymethyl,    hydroxyethyl or hydroxypropyl celluloses grafted, for example, with    a salt chosen from methacryloylethyltrimethylammonium salts,    methacrylamidopropyltrimethylammonium salts and    dimethyldiallylammonium salts;-   (4) cationic polysaccharides, such as those described in U.S. Pat.    Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic    trialkylammonium groups;-   (5) polymers comprising piperazinyl moieties and divalent alkylene    or hydroxyalkylene groups with linear or branched chains, optionally    interrupted by at least one atom chosen from oxygen, sulphur, and    nitrogen atoms or by at least one ring chosen from aromatic and    heterocyclic rings, and the at least one of the oxidation and    quatemization products of said polymers. Such polymers have been    described, for example, in French Patent Nos. 2 162 025 and 2 280    361;-   (6) water-soluble polyaminoamides such as those described in French    Patent Nos. 2 252 840 and 2 368 508;-   (7) polyaminoamide derivatives, for example adipic    acid/dialkylaminohydroxyalkyldialkylene-triamine polymers in which    the alkyl group comprises from 1 to 4 carbon atoms and such as a    methyl, ethyl or propyl group, and the alkylene group comprises from    1 to 4 carbon atoms and such as an ethylene group. Such polymers    have been described, for example, in French Patent No. 1 583 363;-   (8) polymers obtained by reacting a polyalkylene-polyamine    containing two primary amine groups and at least one secondary amine    group, with a dibasic carboxylic acid selected from diglycolic acids    and saturated aliphatic dibasic carboxylic acids comprising from 3    to 8 carbon atoms. The molar ratio between the    polyalkylene-polyamine and the dibasic carboxylic acid is in the    range from about 0.8:1 to about 1.4:1; the resulting polyaminoamide    may be reacted with epichlorhydrin in a molar ratio of    epichlorhydrin to the secondary amine group of the polyaminoamide in    the range from about 0.5:1 to about 1.8:1. Such polymers have been    described, for example, in U.S. Pat. Nos. 3,227,615 and 2,961,347;-   (9) alkyldiallylamine and dialkyldiallylammonium cyclopolymers such    as homopolymer of dimethyldiallylammonium chloride and copolymers of    diallyldimethylammonium chloride and acrylamide;-   (10) quatemary di-ammonium polymers with a number average molar mass    that is generally in the range from about 1000 to about 100,000,    such as those described, for example, in French Patents FR-A-2 320    330, FR-A-2 270 846, FR-A-2 316 271, FR-A-2 336434 and FR-A-2 413    907 and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614,    2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432,    3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653,    4,026,945, and 4,027,020;-   (11) quaternary polyammonium polymers such as those described in    European Patent application EP-A-0 122 324;-   (12) quaternary polymers of vinylpyrrolidone and vinylimidazole such    as those sold by BASF under the trade names Luviquat® FC 905, FC 550    and FC 370;-   (13) polyamines such as Polyquart®) H sold by COGNIS, referred to as    “POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE” in the CTFA dictionary;-   (14) crosslinked polymers of methacryloyloxy(C₁-C₄)alkyl    (C₁-C₄)trialkylammonium salts such as those sold by ALLIED COLLOIDS    under the trade name SALCARE® SC 92, SALCARE® SC 95 and SALCARE® SC    96; and-   (15) mixtures thereof.

Other cationic polymers that can be used are chosen, for example, fromcationic proteins and hydrolysates of cationic proteins,polyalkyleneimines, such as polyethyleneimines, polymers comprisingmoieties chosen from vinylpyridine and vinylpyridinium moieties,condensates of polyamines and epichlorhydrin, quatemary polyureylenes,and chitin derivatives.

Of the cationic polymers mentioned above, quatemary cellulose etherderivatives, cationic cyclopolymers, quaternary polymers ofvinylpyrrolidone and vinylimidazole and mixtures thereof can, forexample, be used.

The compositions can comprise at least one polymer chosen fromamphoteric polymers. Amphoteric polymers that can be used can be chosenfrom polymers comprising moieties B and C statistically distributed inthe polymer chain, wherein B is a moiety deriving from a monomercomprising at least one basic nitrogen atom and C is a moiety derivingfrom an acid monomer comprising at least one group chosen fromcarboxylic and sulphonic groups, or B and C can be groups deriving fromzwitterionic monomers of carboxybetaines or sulphobetaines; B and C canalso be a cationic polymer chain comprising at least one amine groupchosen from primary, secondary, tertiary and quaternary amine groups inwhich at least one of the amine groups carries a carboxylic or sulphonicgroup bonded via a hydrocarbon group, or B and C form part of a chain ofa polymer with an ethylene-αβ-dicarboxylic moiety wherein one of thecarboxylic groups has been reacted with a polyamine containing at leastone-amine group chosen from primary and secondary amine groups.

The amphoteric polymers can, for example, be chosen from the followingpolymers:

(1) polymers resulting from copolymerization of at least one monomerderived from a vinyl compound carrying a carboxylic group, such asacrylic acid, methacrylic acid, maleic acid, and alpha-chloracrylicacid, and at least one basic monomer derived from a substituted vinylcompound comprising at least one basic atom, such as dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkyl methacrylamide, and-acrylamide. Such compounds have been described, for example, in U.S.Pat. No. 3,836,537. The sodiumacrylate/acrylamidopropyltrimethylammonium chloride copolymer sold byCOGNIS as POLYQUART® KE 3033 can, for example, be used. The vinylcompound can also be a dialkyldiallylammonium salt such asdiethyidiallylammonium chloride. Copolymers of acrylic acid and of thelatter monomer have been produced by CALGON under the trade namesMERQUAT® 280, MERQUAT® 295, and MERQUAT® PLUS 3330;

(2) polymers comprising moieties deriving from:

-   -   (a) at least one monomer selected from acrylamides or        methacrylamides substituted on the nitrogen atom with an alkyl        group;    -   (b) at least one acidic comonomer comprising at least one        reactive carboxylic group; and    -   (c) at least one basic comonomer such as esters with        substituents chosen from primary, secondary, tertiary and        quaternary amine substituents of acrylic and methacrylic acids        and the quaternization product of dimethylaminoethyl        methacrylate with dimethyl or diethyl sulphate.

In one embodiment, N-substituted acrylamides or methacrylamides aregroups wherein the alkyl groups comprise from 2 to 12 carbon atoms, suchas N-ethylacrylamide, N-tertiobutylacrylamide, N-tertiooctylacrylamide,N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide, andcorresponding methacrylamides.

The acidic comonomers can be chosen, for example, from acrylic,methacrylic, crotonic, itaconic, maleic, and fumaric acids, as well asalkyl monoesters comprising from 1 to 4 carbon atoms of the maleic orfumaric acids or anhydrides. The basic comonomers are chosen, forexample, from aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl, andN-tertiobutylaminoethyl methacrylates. The copolymers with the CTFAdesignation (4th ed., 1991)“Octylacrylamide/acrylates/butylaminoethyl-methacrylate copolymer” suchas products sold by NATIONAL STARCH under the trade name AMPHOMER® orLOVOCRYL® 47 can be used.

(3) crosslinked and partially or completely alkylated polyaminoamidesderived from polyaminoamides of the general formula:—[—CO—R₁₀—CO—Z—]—  (IV)

in which R₁₀ is a divalent group derived from saturated dibasiccarboxylic acid, mono- and dibasic carboxylic acids comprising anethylenic double bond, an ester of an alkanol comprising from 1 to 6carbon atoms of said acids and a group derived from addition of any oneof said acids with amines chosen from bis-primary or bis-secondaryamines, and Z is a group chosen from bis-primary, mono- andbis-secondary polyalkylene-polyamine groups, and, for example, Zrepresents:

(a) in proportions of from about 60 to about 100 mol %, the group:—NH—[—(CH₂)_(x)—NH—]_(p)—  (V)

in which x=2 and p=2 or 3, or x=3 and p=2; this group being derived froma compound chosen from diethylenetriamine, triethylenetetraamine anddipropylenetriamine;

(b) in proportions of from 0 to about 40 mol %, the group (V) above, inwhich x=2 and p=1 and which is derived from a compound chosen fromethylenediamine and piperazine:

(c) in proportions of from 0 to about 20% by weight, the group—NH—(CH₂)₆—NH—, which is derived from hexamethylenediamine, saidpolyaminoamines being crosslinked by adding a bifunctional crosslinkingagent chosen from epihalohydrins, diepoxides, dianhydrides, andbis-unsaturated derivatives, in an amount of from about 0.025 to about0.35 mol of crosslinking agent per amine group of the polyaminoamide andalkylated by the action of acrylic acid, chloroacetic acid or analkane-sultone or salts thereof.

In one embodiment, the saturated carboxylic acids are, for example,chosen from acids comprising from 6 to 10 carbon atoms such as theadipic acid 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid,terephthalic acid, and acids comprising a double ethylenic bond such asacrylic acid, methacrylic acid, and itaconic acid. The alkane-sultonesused in the alkylation can be chosen, for example, from propane- andbutane-sultones; the alkylation agent salts can be chosen, for example,from sodium and potassium salts.

(4) polymers comprising zwifterionic moieties with formula:

in which R₁₁ is chosen from polymerizable unsaturated groups such as anacrylate, methacrylate, acrylamide and methacrylamide groups, y and z,which may be identical or different, are chosen from integers from 1 to3, R₁₂ and R₁₃, which may be identical or different, are chosen from ahydrogen atom, methyl, ethyl and propyl groups, and R₁₄ and R₁₅, whichmay be identical or different, are chosen from a hydrogen atom and alkylgroups so that the sum of the carbon atoms in R₁₄ and R₁₅ does notexceed 10.

Polymers comprising such moieties can also comprise moieties derivedfrom non-zwitterionic monomers such as monomers chosen from dimethyl-and diethylaminoethyl acrylates and methacrylates, alkyl acrylates andmethacrylates, acrylamides, methacrylamides, and vinyl acetate. By wayof example, mention may be made of the copolymer of methyl methacrylateand methyl dimethylcarboxymethylammonioethylmethacrylate, such as theproduct sold by SANDOZ as DIAFORMER® Z301.

(5) polymers derived from chitosan comprising monomer moieties with thefollowing formulae:

the moiety (VII) being present in proportions in the range from 0 toabout 30%, the moiety (VIII) in proportions in the range from about 5%to about 50%, and the moiety (IX) in proportions in the range from about30% to about 90%, it being understood that in said moiety (IX), R₁₆ is agroup with the formula:

in which q is equal to 0 or 1;

if q=0, R₁₇, R₁₈, and R₁₉, which may be identical or different, arechosen from a hydrogen atom, methyl, hydroxyl, acetoxy and aminoresidues, monoalkylamine residues and dialkylamine residues optionallyinterrupted by at least one nitrogen atom and/or optionally substitutedwith at least one group chosen from amine, hydroxyl, carboxyl, alkylthioand sulphonic groups, and alkylthio residues in which the alkyl groupcarries an amino residue, wherein at least one of groups R₁₇, R₁₈, andR₁₉ in this case is a hydrogen atom; or if q=1, R₁₇, R₁₈, and R₁₉, whichmay be identical or different, are each chosen from a hydrogen atom, andsalts formed by said compounds with bases or acids.

(6) polymers derived from N-carboxyalkylation of chitosan such asN-carboxymethylchitosan and N-carboxybutylchitosan sold by JAN DEKKERunder the trade name EVALSAN®.

(7) polymers corresponding to the general formula (Xl) described, forexample, in French Patent No. 1 400 366:

in which R₂₀ is chosen from a hydrogen atom, CH₃O, CH₃CH₂O and phenylgroups, R₂₁ is chosen from hydrogen and lower alkyl groups such asmethyl and ethyl, R₂₂ is chosen from hydrogen and lower alkyl groupssuch as methyl and ethyl, R₂₃ is chosen from lower alkyl groups such asmethyl and ethyl groups and groups with the formula: —R₂₄—N(R₂₂)₂,wherein R₂₄ is chosen from groups of —CH₂—CH₂—, —CH₂—CH₂—CH₂—, and—CH₂—CH(CH₃)—, and R₂₂ is chosen from hydrogen and lower alkyl groupssuch as methyl and ethyl; and higher homologues of said groupscomprising up to 6 carbon atoms.

(8) amphoteric polymers of the type —D—X—D—X— chosen from:

(a) polymers obtained by the action of chloroacetic acid or sodiumchloroacetate on compounds comprising at least one moiety correspondingto the formula:—D—X—D—X—D—  (XII)

-   -   in which D is a group:

and X is chosen from the symbols E and E′, wherein E and E′, which maybe identical or different, are chosen from alkylene groups with at leastone chain chosen from straight and branched chains comprising from 1 to7 carbon atoms in its main chain, wherein said alkylene groups areunsubstituted or substituted with at least one hydroxyl group. E or E′can optionally also comprise at least one atom chosen from oxygen,nitrogen and sulphur atoms, and 1 to 3 rings chosen from aromatic andheterocyclic cycles. The oxygen, nitrogen, and sulphur atoms can bepresent in the form of at least one group chosen from ether, thioether,sulphoxide, sulphone, sulphonium, alkylamine, alkenylamine, hydroxyl,benzylamine, amine oxide, quatemary ammonium, amide, imide, alcohol,ester and urethane groups.

(b) polymers corresponding to the formula:—D—X—D—X—  (XIII)

-   -   in which D is a group:

and X is chosen from the symbols E and E′, and wherein at least one X ischosen from E′; E having the meaning given above and E′ being a divalentalkylene group with at least one chain chosen from straight and branchedchains comprising from 1 to -7 carbon atoms in the main chain, whereinsaid divalent alkylene group is unsubstituted or substituted with atleast one hydroxyl group and comprises at least one nitrogen atom, thenitrogen atom being substituted with an alkyl chain which is optionallyinterrupted by an oxygen atom, wherein said alkyl chain comprises atleast one functional group chosen from carboxyl functional groups andhydroxyl functional groups and wherein said alkyl chain is betainized byreaction with a reactant chosen from chloroacetic acid and sodiumchloroacetate.

-   (9) alkyl(C₁-C₅)vinyl ether/maleic anhydride copolymers partially    modified by semiamidation with an N,N-dialkylaminoalkylamine such as    N,N-dimethylaminopropylamine or by semi-esterification with an    N,N-dialkanolamine. These copolymers can also comprise other vinyl    compounds such as vinylcaprolactam.

In one embodiment, the amphoteric polymers are chosen from polymers offamily (1).

Additionally, the compositions can comprise at least one polymer chosenfrom anionic polymers, which are either soluble or dispersed. Examplesof the anionic polymers are chosen from polymers comprising carboxylic,sulphonic and phosphoric groups, and can have a mass average or numberaverage molecular mass in the range from about 500 to about 5,000,000.

The carboxylic groups are derived from unsaturated monoacidic or dibasiccarboxylic acid monomers, such as those corresponding to the followingformula:

In which:

-   n is an integer ranging from 0 to 10;-   A is a methylene group, optionally bonded to the carbon atom of the    unsaturated group or to the neighbouring methylene group when n is    greater than 1 via a hetero atom such as oxygen or sulphur;-   R₁ is chosen from a hydrogen atom, and phenyl and benzyl groups;-   R₂ is chosen from a hydrogen atom, alkyl groups comprising from 1 to    6 carbon atoms and carboxyl groups; and-   R₃ is chosen from a hydrogen atom, alkyl groups comprising from 1 to    6 carbon atoms, and —CH₂—COOH, phenyl and benzyl groups.

In formula (XIV) above, the alkyl groups comprise, for example, from 1to 4 carbon atoms, such as methyl and ethyl groups.

The anionic polymers with carboxylic groups are chosen, for example,from:

A) homo- and copolymers of acrylic and methacrylic acid and their salts,such as products sold by ALLIED COLLOID under the trade name VERSICOL® Eor K, or by BASF under the trade name ULTRAHOLD®, and acrylic acid andacrylamide copolymers sold by HERCULES in the form of their sodium saltunder the trade names RETEN® 421, 423 or 425, the sodium salts ofpolyhydroxycarboxylic acids;

B) copolymers of acrylic and methacrylic acid with a monoethylenicmonomer such as ethylene, styrene, vinyl esters, acrylic and methacrylicesters, optionally grafted to a polyalkylene glycol, such aspolyethylene glycol, and optionally crosslinked. Such polymers have, forexample, been described in French Patent FR-A-1 222 944 and GermanPatent Application DE-A-2 330 956, copolymers of that type comprising intheir chain an acrylamide moiety, optionally N-alkylated and/orhydroxyalkylated as described, for example, in Luxembourg PatentApplications L-A-75370 and 75371 or sold by AMERICAN CYANAMID under thetrade name QUADRAMER®. Also included are copolymers of acrylic acid andC₁-C₄ alkyl methacrylate and the copolymer of methacrylic acid and ethylacrylate sold by BASF as LUVIMER® MAEX.

C) copolymers derived from crotonicsacid, such as those comprising vinylacetate or propionate moieties in their chain, and optionally othermonomers such as allyl and methallyl esters, vinyl ethers and vinylesters of an acid chosen from linear and branched, saturatedlong-hydrocarbon-chain carboxylic acids such as those containing atleast 5 carbon atoms, said polymers optionally being grafted andcrosslinked, or a vinyl, allyl and methallyl esters of an α- or β-cycliccarboxylic acid. These polymers have, inter alia, been described inFrench Patents FR-A-1 222 944, FR-A-1 580 545, FR-A-2 265 782, FR-A-2265 781, FR-A-1 564 110, and FR-A-2 439 798. Commercially availableproducts included in this class are resins 28-29-30, 26-13-14 and28-13-10 sold by NATIONAL STARCH.

D) polymers derived from maleic, fumaric or itaconic acids or anhydrideswith vinyl esters, vinyl ethers, vinyl halides, phenyl vinylderivatives, acrylic acid and its esters; said polymers may beesterified. Such polymers have been described, for example, in U.S. Pat.Nos. 2,047,398, 2,723,248, 2,102,113, United Kingdom Patent GB-A-839805, andinclude those sold by ISP under the trade names GANTREZ® AN orES.

Polymers that also fall within this class are copolymers of maleic,citraconic or itaconic anhydrides with an allyl or methallyl esteroptionally comprising at least one group chosen from acrylamide,methacrylamide, α-olefin, acrylic and methacrylic esters, acrylic andmethacrylic acids and vinylpyrrolidone groups in their chain, theanhydride functions optionally being monoesterified or monoamidified.Such polymers have, for example, been described in French Patents FR-A-2350 384 and FR-A-2 357 241.

E) Polyacrylamides comprising carboxylate groups.

Polymers comprising sulphonic groups are polymers comprising at leastone moiety chosen from vinylsulphonic, styrenesulphonic,naphthalenesulphonic and acrylamidoalkylsulphonic moieties. Saidpolymers can, for example, be chosen from:

-   -   (a) polyvinylsulphonic acid salts with a molar mass in the range        from about 1000 to about 100,000 and copolymers with an        unsaturated comonomer such as acrylic and methacrylic acid and        their esters, as well as acrylamide and its derivatives, vinyl        ethers and vinylpyrrolidone;    -   (b) polystyrenesulphonic acid salts and sodium salts with        molecular weights of about 500,000 and about 100,000,        respectively, sold by NATIONAL STARCH under the trade names        FLEXAN® 500 and FLEXAN® 130. Said compounds have been described        in French Patent FR-A-2 198 719;    -   (c) polyacrylamide-sulphonic acid salts such as those mentioned        in U.S. Pat. No. 4,128,631, for example,        polyacrylamidoethylpropanesulphonic acid sold by COGNIS as        COSMEDIA POLYMER® HSP 1180.

The anionic polymers are, for example, selected from acrylic acidcopolymers such as the acrylic acid/ethylacrylate/N-tertiobutylacrylamide terpolymer sold by BASF under the tradename ULTRAHOLD STRONG®, copolymers derived from crotonic acid such asvinyl acetate/vinyl tertiobutylbenzoate/crotonic acid terpolymers andcrotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold byNATIONAL STARCH under the trade name RESINE 28-29-30, polymers derivedfrom maleic, fumaric or itaconic acids or anhydrides with vinyl esters,vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid andits esters such as the monoesterified methyl vinyl ether/maleicanhydride copolymer sold by ISP under the trade name GANTREZ® ES 425,copolymers of methacrylic acid and methyl methacrylate sold by ROHMPHARMA under the trade name EUDRAGIT® L, the copolymer of methacrylicacid and ethyl acrylate sold by BASF under the trade name LUVIMER® MAEX,the vinyl acetate/crotonic acid copolymer sold by BASF under the tradename LUVISET® CA 66 and the vinyl acetate/crotonic acid/polyethyleneglycol terpolymer sold by BASF under the trade name ARISTOFLEX®.

The anionic polymers are further, for example, chosen from themonoesterified maleic methyl vinyl ether/maleic anhydride copolymer soldby ISP under the trade name GANTREZ® ES 425, copolymers of methacrylicacid and. methyl methacrylate sold by ROHM PHARMA under the trade nameEUDRAGIT®, the copolymer of methacrylic acid and ethyl acrylate sold byBASF under the trade name LUVIMER® MAEX, and thevinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymer sold by ISPunder the trade name ACRYLIDONE® LM.

It is also possible to use anionic polymers in the form of latex orpseudolatex, i.e., in the form of an aqueous dispersion of insolublepolymer particles.

The compositions can comprise at least one polymer chosen from solubleand dispersed nonionic polymers. These may include:

-   (1) vinylpyrrolidone homopolymers;-   (2) copolymers of vinylpyrrolidone and vinyl acetate;-   (3) polyalkyloxazolines, such as polyethyloxazolines sold by DOW    CHEMICAL under the trade names PEOX® 50 000, PEOX® 200 000, and    PEOX® 500 000;-   (4) vinyl acetate homopolymers such as the product sold by HOECHST    under the trade name APPRETAN® EM or the product sold by RHODIA    under the trade name RHODOPAS® A 012;-   (5) copolymers of vinyl acetate and an acrylic ester, such as the    product sold by RHODIA under the trade name RHODOPAS® AD 310;-   (6) copolymers of vinyl acetate and ethylene, such as the product    sold by HOECHST under the trade name APPRETAN® TV;-   (7) copolymers of vinyl acetate and a maleic ester, for example    dibutyl maleate, such as the product sold by HOECHST under the trade    name APPRETAN® MB EXTRA;-   (8) copolymers of polyethylene and maleic anhydride;-   (9) alkyl acrylate homopolymers and alkyl methacrylate homopolymers,    such as the product sold by MATSUMUTO under the trade name    MICROPEARL® RQ 750 or the product sold by BASF under the trade name    LUHYDRAN® A 848 S;-   (10) acrylic ester copolymers, such as copolymers of alkyl acrylates    and alkyl methacrylates, for example, the products sold by ROHM &    HMS under the trade names PRIMAL® AC-261 K and EUDRAGIT® NE 30 D, by    BASF under the trade names ACRONALOR® 601, LUHYDRAN® LR 8833 or    8845, by HOECHST under the trade names APPRETAN® N 9213 or N9212;-   (11) copolymers of acrylonitrile and a nonionic monomer selected,    for example, from butadiene and alkyl (meth)acrylates; products sold    by NIPPON ZEON under the trade name NIPOL® LX 531 8 or those sold by    ROHM & HMS under the trade name CJ 0601 8;-   (12) polyurethanes, such as the products sold by ROHM & HAAS under    the trade names ACRYSOL® RM 1020 or ACRYSOL® RM 2020, or products    sold by DSM RESINS under the trade names URAFLEX® XP 401 UZ,    URAFLEX) XP 402 UZ;-   (13) copolymers of alkyl acetate and urethane, such as NATIONAL    STARCH's product 8538-33;-   (14) polyamides, such as the product sold by RHONE POULENC under the    trade name ESTAPOR® LO 11; and-   (15) chemically modified or unmodified nonionic guar gums.

Unmodified nonionic guar gums that can be used include the product soldby UNIPECTINE under the trade name VIDOGUM® GH 175 and the product soldby MEYHALL under the trade name JAGUAR®) C. Modified nonionic guar gumsthat can be used include guar gums modified by C₁-C₆ hydroxyalkylgroups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl orhydroxybutyl groups. Such guar gums are well known in the art and can,for example, be prepared by reacting the oxides of correspondingalkenes, such as propylene oxides, with guar gum to obtain a guar gummodified with hydroxypropyl groups. Examples of such nonionic guar gumsoptionally modified with hydroxyalkyl groups are those sold by RHODIAunder the trade names JAGUAR® HP 8, JAGUAR(® HP 60, JAGUAR® HP 120,JAGUAR® DC 293, and JAGUAR® HP 105, or by AQUALON under the trade nameGALACTASOL® 4H4FD2.

The alkyl groups of the nonionic polymers, for example, comprise from 1to 6 carbon atoms.

Additionally, the compositions can comprise at least one silicone. Theat least one silicone that can be used may be soluble or insoluble inthe compositions. For example, the at least one silicone can be chosenfrom polyorganosiloxanes that are insoluble in the compositions; theycan be in the form of oils, waxes, resins or gums. Polyorganosiloxanesare described in more detail in Walter Noll, “Chemistry And Technologyof Silicones” (Academic Press, 1968).

The silicones may be volatile or non-volatile. When they are volatile,the silicones are, for example, chosen from those with a boiling pointin the range of from about 60° C. to about 260° C., and further, forexample, may be chosen from:

(1) cyclic silicones comprising from 3 to 7 silicon atoms, such as 4 or5 silicone atoms. Examples include octamethylcyclotetrasiloxane sold byUNION CARBIDE under the trade name VOLATILE SILICONE 7207 or by RHODIAunder the trade name SILBIONE 70045 V2, and decamethylcyclopentasiloxanesold by UNION CARBIDE under the trade name VOLATILE SILICONE 7158, or byRHODIA under the trade name SILBIONE 70045 V 5, and mixtures thereof.

Other examples include cyclopolymers of thedimethylsiloxane/methylalkylsiloxane type such as SILICONE VOLATILE FZ3109 sold by UNION CARBIDE, which has the following chemical structure:

Still other examples include mixtures of cyclic silicones with organiccompounds derived from silicon, such as a mixture ofoctamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol(50/50) or a mixture of octamethylcyclotetrasiloxane andoxy-1,1′-(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy) bis-neopentane; and

(2) volatile linear silicones comprising from 2 to 9 silicon atoms andwith a viscosity of less than or equal to about 5×10⁻⁶ m²/s at 25° C.Examples include decamethyltetrasiloxane sold by TORAY SILICONE underthe trade name SH 200. Silicones in this class have also been describedin Todd & Byers, “Volatile silicone fluids for cosmetics,” 91 Cosmeticsand Toiletries, pp. 27-32 (January 1976).

Non-volatile silicones including polyalkylsiloxanes, polyarylsiloxanes,polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanesmodified by organofunctional groups, and mixtures thereof may also beused.

Organomodified silicones that can be used are silicones as defined aboveand comprising in their structure at least one organofunctional groupfixed via a hydrocarbon group. Examples of organomodified siliconesinclude polyorganosiloxanes comprising at least one group chosen from:

-   (1) polyethyleneoxy and polypropyleneoxy groups optionally    comprising C₆-C₂₄ alkyl groups such as dimethicone-copolyol products    sold by DOW CORNING under the trade name DC 1248 or SILWET® L 722, L    7500, L 77, L 711 from UNION CARBIDE and alkyl    (C₁₂)methicone-copolyol sold by DOW CORNING under the trade name Q2    5200;-   (2) amine groups, which may or may not be substituted, such as the    products sold by GENESEE under the trade name GP 4 Silicone Fluid    and GP 7100 or products sold by DOW CORNING under the trade name Q2    8220 and DOW CORNING 929 or 939. For example, the substituted amine    groups are chosen from C₁-C₄ aminoalkyl groups;-   (3) thiol groups, such as the products sold by GENESEE under the    trade name GP 72 A and GP 71;-   (4) alkoxylated groups, such as the product sold by SWS SILICONES    under the trade name SILICONE COPOLYMER F-755 and by GOLDSCHMIDT    under the trade name ABIL WAX®) 2428, 2434, and 2440;-   (5) hydroxylated groups, such as polyorganosiloxanes with a    hydroxyalkyl function as described in French Patent Application    FR-A-85 16334;-   (6) acyloxyalkyl groups, such as polyorganosiloxanes as described in    U.S. Pat. No. 4,957,732;-   (7) anionic groups of the carboxylic acid type, such as the products    described in EP-A-0 186 507 from CHISSO CORPORATION, or of the    alkylcarboxylic type such as those present in the product X-22-3701    E from SHIN-ETSU; 2-hydroxyalkylsulphonate; or    2-hydroxyalkylthiosulphate, such as the products sold by GOLDSCHMIDT    under the trade names ABIL® S201 and ABIL® S255; and-   (8) hydroxyacylamino groups, such as polyorganosiloxanes described    in European Patent EP-A-0 342 834, such as those sold by DOW CORNING    under the trade name Q2-8413.

It is also possible to use grafted silicones with a hydrocarbon skeletonand silicone grafts or a silicone skeleton and hydrocarbon grafts, suchas the product sold by 3M under the trade name VS80.

The compositions can additionally comprise at least one oil chosen frommineral, vegetable and animal oils. Oils of vegetable origin include,for example, sweet almond oil, avocado oil, castor oil, olive oil,jojoba oil, sunflower seed oil, wheatgerm oil, sesame seed oil, peanutoil, grapeseed oil, soya oil, rapeseed oil, carthame oil, coprah oil,corn oil, hazelnut oil, shea butter, palm oil, apricot kernel oil andcalophyllum oil. An oil of animal origin is, for example,perhydrosqualene. Oils of mineral origin include, for example, paraffinoil and vaseline oil.

The compositions can comprise at least one compound chosen frompolyisobutenes and poly(α-olefins), chosen from those that are wellknown in the art.

The compositions can further comprise at least one surfactant chosenfrom anionic, amphoteric, nonionic and cationic surfactants. Examples ofanionic surfactants that can be used alone or as a mixture include, forexample, salts (such as alkaline salts, for example, sodium salts,ammonium salts, amine salts, aminoalcohol salts and magnesium salts) ofthe following compounds: alkyl sulphates, alkyl ether sulphates,alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceridesulphates; alkyl sulphonates, alkyl phosphates, alkylamide sulphonates,alkylaryl sulphonates, α-olefin sulphonates, paraffin sulphonates; alkylsulphosuccinates, alkyl ether sulphosuccinates, alkylamidesulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates; alkylether phosphates; acyl sarcosinates; acyl isethionates, acyl glutamatesand N-acyl taurates. The alkyl or acyl radical in all of these differentcompounds comprise, for example, from 12 to 20 carbon atoms and the arylradical is, for example, chosen from phenyl and benzyl groups. Anionicsurfactants that can be used include, for example, salts of fatty acidssuch as the salts of oleic acids, ricinoleic acids, palmitic acids,stearic acids, coprah oil acids or hydrogenated coprah oil acids andacyl lactylates wherein the acyl radical comprises from 8 to 20 carbonatoms. It is also possible to use weakly anionic surfactants such asalkyl D galactoside uronic acids and their salts and polyoxyalkylenated(C₆C₂₄)alkyl ether carboxylic acids, polyoxyalkylenated (C₆-C₂₄)alkylaryl ether carboxylic acids, polyoxyalkylenated (C₆-C₂₄)alkyl amidoether carboxylic acids, and salts thereof, for example, those comprisingfrom 2 to 50 ethylene oxide groups, and mixtures thereof. The anionicsurfactants include, for example, alkyl sulphate and alkyl ethersulphate salts and their mixtures.

Nonionic surfactants that can be used are chosen, for example, fromalcohols, alpha-diols, alkylphenols and polyethoxylated,polypropoxylated and polyglycerolated fatty acids with a fatty chaincomprising from 8 to 18 carbon atoms, for example, the number ofethylene oxide or propylene oxide groups possibly ranging, for example,from 2 to 50 and the number of glycerol groups possibly ranging, forexample, from 2 to 30. Nonionic surfactants may also include copolymersof ethylene oxide and propylene oxide, condensates of ethylene oxide andpropylene oxide on fatty alcohols; polyethoxylated fatty amides, forexample, those comprising from about 2 to about 30 mol of ethyleneoxide, polyglycerolated fatty amides comprising an average of from 1 to5 glycerol groups, and such as from 1.5 to 4 glycerol groups;polyethoxylated fatty amines, such as those comprising from about 2 toabout 30 mol of ethylene oxide; fatty acid esters of oxyethylenatedsorbitan comprising from about 2 to about 30 mol of ethylene oxide;fatty acid esters of saccharose, fatty acid esters of polyethyleneglycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxidessuch as alkyl(C₁₀-C₁₄) amines or N-acylaminopropylmorpholine oxides.

Amphoteric surfactants that can be used are chosen, for example, fromderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical is chosen from linear and branched chains comprisingfrom 8 to 22 carbon atoms and comprising at least one hydrosolubilizinganionic group (for example carboxylate, sulphonate, sulphate, phosphateand phosphonate); additional examples include (C₈-C₂₀)alkyl betaines,sulphobetaines, (C₈-C₂₀)alkyl amido (C₁-C₆)alkylbetaines such ascocoamidopropylbetaines or (C₈-C₂₀)alkyl amido(C₁-C₆)alkylsulphobetaines.

Among the amine derivatives, mention may be made of the products soldunder the trade name MIRANOL®, as described in U.S. Pat. Nos. 2,528,378and 2,781,354 with structures of:R₂—CONHCH₂CH₂N⁺(R₃)(R4)(CH₂COO⁻)

-   -   in which R₂ is chosen from alkyl radicals derived from an acid        R₂—COOH present in hydrolysed coprah oil, and heptyl, nonyl and        undecyl radicals; R₃ is a beta-hydroxyethyl group; and R₄ is a        carboxymethyl group; and of        R′₂—CONHCH₂CH₂—N(B)(C)

in which B represents —CH₂CH₂OX′, in which X′ is chosen from—CH₂CH₂—COOH group and a hydrogen atom; C represents —(CH₂)_(z)—Y′wherein z=1 or 2 and Y′ is chosen from —COOH and —CH₂—CHOH—SO₃H; and R′₂is chosen from alkyl radicals of an acid R′₂—COOH present in coprah oilor in hydrolysed linseed oil, and alkyl radicals, such as C₇, C₉, C₁₁and C₁₃ alkyl radicals, a C₁₇ alkyl radical and its iso-form, and anunsaturated C₁₇ radical. These compounds are classified in the CTFAdictionary (5th ed., 1993), under the denominations DisodiumCocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium.Caprylamphodiacetate, Disodium Capryloamphodiacetate, DisodiumCocoamphodipropionate, Disodium Lauroamphodipropionate, DisodiumCaprylamphodipropionate, Disodium Capryloamphodipropionate,Lauroamphodipropionic acid, and Cocoamphodipropionic acid. One exampleis cocoamphodiacetate, sold by RHODIA CHIMIE under the trade nameMIRANOL® C2M concentrate.

Cationic surfactants that can be used are chosen, for example, fromsalts of primary, secondary or tertiary fatty amines, optionallypolyoxyalkylenated; quaternary ammonium salts; imidazoline derivatives;or amine oxides with a cationic nature. The quatemary ammonium saltsare, for example, chosen from:

(1) quaternary ammonium salts with the following general formula (XV):

in which the radicals R₁ to R₄, which may be identical or different, arechosen from linear and branched aliphatic radicals comprising from 1 to30 carbon atoms and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals can comprise at least one hetero atom such as oxygen,nitrogen, sulphur and halogens. The aliphatic radicals are, for example,chosen from alkyl, alkoxy, polyoxy(C₂-C₆)alkylene, alkylamide,(C₁₂-C₂₂)alkylamido (C₂-C₆)alkyl, (C₁₂-C₂₂)alkylacetate and hydroxyalkylradicals, comprising from 1 to 30 carbon atoms. X⁻ is an anion chosenfrom halides, phosphates; acetates, lactates, alkyl(C₂-C₆)sulphates,alkyl and alkylarylsulphonates;

(2) quaternary ammonium salts of imidazolinium, such as those with thefollowing formula (XVI):

in which R₅ is chosen from alkenyl and alkyl radicals comprising from 8to 30 carbon atoms, for example, tallow fatty acid derivatives, R₆ ischosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl and alkylradicals comprising from 8 to 30 carbon atoms, R₇ is chosen from C₁-C₄alkyl radicals, R8 is chosen from a hydrogen atom, and C₁-C₄ alkylradicals, X⁻ is an anion chosen from halides, phosphates, acetates,lactates, alkylsulphates, alkyl- and alkylarylsulphonates. In oneembodiment, R₅ and R₆ are, for example, a mixture of radicals chosenfrom alkenyl and alkyl radicals comprising from 12 to 21 carbon atoms,such as tallow fatty acid derivatives, R₇ is methyl, and R₈ is hydrogen.An example of such a product is sold by REWO under the trade nameREWOQUAT W 75;

(3) quaternary diammonium salts with the formula (XVII):

in which R₉ is chosen from aliphatic radicals comprising from 16 to 30carbon atoms, R₁₀, R₁₁, R₁₂, R₁₃, and R₁₄, which may be identical ordifferent, are chosen from hydrogen and alkyl radicals comprising from 1to 4 carbon atoms; X⁻ is an anion chosen from halides, acetates,phosphates, nitrates, and methylsulphates. Such quaternary diammoniumsalts include, for example, diammonium propanetallow dichloride;

(4) quaternary ammonium salts comprising at least one ester function,such as those with the following formula (XVIII):

In which:

R₁₅ is chosen from linear and branched C₁-C₆ alkyl radicals and C₁-C₆hydroxyalkyl and dihydroxyalkyl radicals;

-   R₁₆ is chosen from hydrogen; the radical R₁₉—CO—, in which R₁₉ is    chosen from linear and branched, saturated and unsaturated C₇-C₂₁    hydrocarbon radicals; and linear and branched, saturated and    unsaturated C₁-C₂₂ hydrocarbon radicals;-   R₁₇ is chosen from linear and branched, saturated and unsaturated    C₇-C₂₁, hydrocarbon radicals;-   R₁₈ is chosen from hydrogen; the radical R₂₀—CO—, in which R₂₀ is    chosen from linear and branched, saturated and unsaturated C₇-C₂,    hydrocarbon radicals; and linear and branched, saturated and    unsaturated C₁-C₆ hydrocarbon-radicals;-   n, p, and r, which may be identical or different, are integers    chosen from 2 to 6;-   X⁻ is an anion chosen from simple and complex organic and inorganic    anions;-   x and z, which may be identical or different, are integers chosen    from 0 to 10;-   y is an integer chosen from 1 to 10;-   wherein the sum x+y+z is from 1 to 15; with    the proviso that (1) when x=0, then R₁₆ is chosen from linear and    branched, saturated and unsaturated C₁-C₂₂ hydrocarbon radicals;    and (2) that when z=0, then R₁₈ is chosen from linear and branched,    saturated and unsaturated C₁-C₆ hydrocarbon radicals.

In one embodiment, the R₁₅, alkyl radicals are linear and are chosen,for example, from methyl, ethyl, hydroxyethyl and dihydroxypropylradicals, such as methyl and ethyl radicals., In another embodiment, thesum x+y+z is from 1 to 10. In another embodiment, when R₁₆ is chosenfrom linear and branched, saturated and unsaturated C₁-C₂₂ hydrocarbonradicals, it may, for example, contain 12 to 22 carbon atoms or 1 to 3carbon atoms. When R₁₈ is chosen from linear and branched, saturated andunsaturated C₁-C₆ hydrocarbon radicals, it may, for example, contain 1to 3 carbon atoms.

In one embodiment, R₁₇, R₁₉, and R₂₀, which may be identical ordifferent, are chosen from linear and branched, saturated andunsaturated C₁₁-C₂, hydrocarbon radicals, such as from linear andbranched, saturated and unsaturated C₁₁-C₂, alkyl and alkenyl radicals.In another embodiment, x and z, which may be identical or different,equal 0 or 1. For example, y equals 1. And N, p, and r, which may beidentical or different, are, for example, 2 or 3 and further, forexample, equal to 2.

Anion X⁻ is chosen, for example, from halides (such as chloride, bromideand iodide) and alkylsulphates such as methylsulphate. But it ispossible to use the methanesulphonate, phosphate, nitrate, tosylate, ananion derived from an organic acid such as an acetate or lactate or anyother anion that is compatible with the ammonium with the esterfunction. For example, anion X⁻ is chosen from chloride andmethylsulphate.

In one embodiment, the ammonium salts with formula (XVIII) can be one,in which:

-   R₁₅ is chosen from methyl and ethyl radicals;-   x and y equal 1;-   z equals 0 or 1;-   n, p, and r equal 2;-   R₁₆ is chosen from hydrogen; the radical R₁₉—CO—, in which R₁₉ is    chosen from linear and branched, saturated and unsaturated C₁₃-C₁₇    hydrocarbon radicals; methyl and ethyl radicals, and linear and    branched, saturated and unsaturated C₁₄-C₂₂ hydrocarbon radicals;-   R₁₇ is chosen from linear and branched, saturated and unsaturated    C₁₃-C₁₇ hydrocarbon radicals; and-   R₁₈ is chosen from hydrogen and radicals of R₂₀—CO—, in which R₂₀ is    chosen from linear and branched, saturated and unsaturated C₁₃-C₁₇    hydrocarbon radicals.

The hydrocarbon radicals are, for example, linear. Compounds withformula (XVIII) include salts (such as chloride and methylsulphate) ofdiacyloxyethyl dimethyl ammonium, diacyloxyethyl hydroxyethyl methylammonium, monoacyloxyethyl dihydroxyethyl methyl ammonium,triacyloxyethyl methyl ammonium, monoacyloxyethyl hydroxyethyl dimethylammonium, and mixtures thereof. The acyl radicals, for example, comprisefrom 14 to 18 carbon atoms and originate from vegetable oil such. aspalm oil or sunflower seed oil. When the compound comprises a pluralityof acyl radicals, the acryl radicals can be identical or different.

These compounds are obtained, for example, by direct esterification oftriethanolamine, triisopropanolamine, alkyldiethanolamine oralkyidiisopropanolamine, optionally oxyalkylenated on fatty acids or onmixtures of fatty acids of vegetable or animal origin or bytransesterification of their methyl esters. This esterification isfollowed by quaternization using an alkylating agent such as an alkylhalide (for example, methyl and ethyl), a dialkyl sulphate (for example,methyl and ethyl), methyl methanesulphonate, methylpara-toluenesulphonate, glycol chlorohydrin and glycerol. Compounds ofthis type include, for example, those sold by COGNIS under the tradename DEHYQUART, by STEPAN under the trade name STEPANQUAT, by CECA underthe trade name NOXAMIUM and by REWO-WITCO under the trade name REWOQUATWE 18.

It is also possible to use ammonium salts containing at least one esterfunction as described in U.S. Pat. Nos. 4,874,554 and 4,137,180.Quaternary ammonium salts of formula (XV) include, for example,tetraalkylammonium chlorides such as dialkyldimethylammonium oralkyltrimethylammoniuhi chlorides, in which the alkyl radical comprisesfrom 12 to 22 carbon atoms, such as behenyltrimethylammonium chlorides,distearyldimethylammonium chloride, cetyltrimethylammonium chloride,benzyldimethylstearylammonium chloride, or stearamidopropyldimethyl(myristyl acetate)ammonium chloride sold by VAN DYK under the trade nameCERAPHYL 70.

In the compositions, it is, for example, possible to use mixtures ofsurfactants, such as mixtures of at least one anionic surfactant and atleast one surfactant chosen from amphoteric and nonionic surfactants.For example, a mixture of at least one anionic surfactant and at leastone amphoteric surfactant can be used.

The anionic surfactants are, for example, compounds chosen from sodium,triethanolamine and ammonium (C₁₂-Cl₄)alkylsulphates, sodium(C₁₂-C₁₄)alkylethersulphates oxyethylenated with about 2.2 mol ofethylene oxide, sodium cocoyl isethionate and sodiumalpha(C₁₄-C₁₆)olefin sulphonate and mixtures thereof with:

-   (1) either at least one amphoteric surfactant such as amine    derivatives , for example, disodium cococamphodipropionate or sodium    cocoamphopropionate, sold, for example, by RHODIA CHIMIE under the    trade name MIRANOL® C2M CONC in aqueous solution with an active    content of 38% or under the trade name MIRANOL® C32;-   (2) or at least one amphoteric zwitterionic-type surfactant such as    alkylbetaines, for example, cocoylbetaine sold by COGNIS under the    trade name DEHYTON® AB 30 in aqueous solution with a 32% active    content or alkyl amidoalkylbetaines such as TEGOBETAINE® F 50, sold    by GOLDSCHMIDT.

The compositions can also comprise at least one adjuvant chosen-fromadjuvants normally used in the cosmetic or dermatological fields, suchas gelling agents and thickening agents, which may or may not beassociative, of a nonionic nature such as polyurethanes, anionic,cationic or amphoteric in nature; moisturizing agents; emollients;insect repellents; thinning agents; preservatives; alkanizing andacidifying agents; fragrances; mineral and organic fillers; colorants;mineral and organic salts; vitamins; enzymes; hormones; antiparasiticagents, anti-acne agents, antiperspirant, keratolytic agents,anti-alopecia agents, and agents countering pigmentation problems.

One of ordinary skill in the art will carefully select any complementarycompounds and/or their quantity so that the advantageous propertiesintrinsically pertaining to the composition disclosed herein are not, orare not substantially, altered by the envisaged addition. In general,complementary compounds can be present with any one compound beingpresent in a quantity ranging from 0 to about 20% by weight relative tothe total composition weight.

The compositions can be in any suitable form for topical application,such as in the form of lotion- or serum-type solutions; aqueous gels;emulsions obtained by dispersing a fatty phase in an aqueous phase (O/W)or conversely (W/O), with a liquid, semi-liquid or solid consistencysuch as a milk, cream of greater or lesser oiliness, or a paste. Thesecompositions are prepared using the usual processes known in the field.

Additionally, the compositions can be used as rinse or no-rinse haircareproducts, such as for washing, care, conditioning, and maintaininghairstyle and for shaping keratinous fibres (such as the hair). They canbe hairstyling products such as setting lotions, blow-drying lotions,fixing, and styling compositions. The lotions can be packaged in avariety of forms, such as sprays, pumps or in aerosol receptacles toensure application of the composition in spray or mousse form. Suchpackaging forms are indicated, for example, when a spray or mousse forfixing or for treating the hair is required. The compositions can alsobe used as shampoos, rinse or no-rinse compositions, for applicationbefore or after a shampoo, a colorant, a bleach, a permanent or astraightening treatment.

The compositions can also be used as a skin care and/or hygiene productfor the face or body, such as creams for protection, treatment or careof the face, hands or body, body milks for protection or for care,lotions, gels or mousses for care of the skin and the mucous membranesor for cleaning the skin.

The compositions can be used as an antisun product. The compositions canalso consist of solid preparations constituting soaps or cleaning bars.

Furthermore, the compositions can be used as bucco-dental care productssuch as toothpastes or mouthwashes.

Finally, the compositions can be used as makeup products such as facecreams, foundations, mascaras, eyeliners or lipsticks.

Illustrative, but non-limiting, examples are set forth below.

EXAMPLE 1

Preparation of a Wheat Starch Betainate Chloride (First Process)

(A compound of formula (I) in which Y is a starch residue, A is —CH₂—,R₁=R₂=R₃=methyl, and X⁻ is Cl⁻).

1.52 ml of N,N′-diisopropylcarbodiimide (9.88 mmol), 0.15 g of4-dimethylaminopyridine (1.23 mmol), and 0.33 g of hydroxybenzotriazole(2.47 mmol) were added in succession to a solution of native wheatstarch (1 g, 6.17 mmol) and N,N-dimethylglycine (0.29 g, 2.81 mmol) in40 ml of anhydrous DMSO. The mixture was stirred in nitrogen at ambienttemperature for 12 hours, then the reaction was stopped by adding 1 mlof water. The mixture was poured into 400 ml of ethanol to precipitateout the starch ester that had formed. The white precipitate was washedwith acetone and vacuum-dried at ambient temperature to give 0.85 g ofstarch poly(N,N-dimethylglycyl)ester (yield: 74%) with a degree ofsubstitution of 0.3.

1 ml of methyl iodide (16 mmol) was added to a solution of 0.75 g ofstarch poly(N,N-dimethylglycyl)ester (4 mmol) in 15 ml of anhydrousDMSO. The mixture was stirred in the dark and under nitrogen for 5 hoursat ambient temperature. It was then poured into 300 ml of ethanol toprecipitate out the starch betainate.

The yellow precipitate was dissolved in 100 ml of water and 50 ml of anaqueous 0.05 M NaCl solution was added. The solution was ultrafilteredthrough an Amicon PM10 membrane in an Amicon 8200 cell provided with anAmicon RS4 reservoir filled with 750 ml of 0.01M NaCl and pure water.Ultrafiltration was stopped when the conductivity of the filtrate wasless than 10 μS. The starch betainate chloride was then recovered in theform of a white powder by freeze-drying.

0.72 g of wheat starch betainate chloride (yield: 89%) was obtained witha degree of substitution of 0.3, determined by proton NMR.

EXAMPLE 2

Preparation of a Wheat Starch Betainate Chloride from Betainyl Chloride(Second Process)

(A compound of formula (I) in, which Y is a starch residue, A is —CH₂—,R₁=R₂=R₃=methyl, and X⁻ is Cl⁻).

1.59 ml of N,N′-diisopropylcarbodiimide (10.3 mmol), 0.156 g of4-dimethylaminopyridine (1.284 mmol) and 0.347 g of hydroxybenzotriazole(2.57 mmol) were added in succession to a solution of native wheatstarch (1.04 g, 6.42 mmol) and betainyl chloride (0.394 g, 2.57 mmol) in40 ml of anhydrous DMSO. The mixture was stirred in nitrogen at ambienttemperature for 12 hours, then the reaction was stopped by adding 1 mlof water. The mixture was then poured into 400 ml of ethanol.

The suspension was centrifuged at 1000 rpm for 12 minutes. The whiteprecipitate was removed and washed three times with ethanol. Theprecipitate was then dissolved in 100 ml of water and the solution wasfiltered through a Sartorius membrane (pore size 8 to 3 μm).

The wheat starch betainate chloride was recovered by freeze-drying inthe form of a white powder (0.88 g, yield; 75%).

EXAMPLE 3

Preparation of a Maltodextrin Betainate Chloride

(A compound of formula (I) in which Y is a maltodextrin residue, A is—CH₂—, R₁=R₂=R₃=methyl, and X⁻ is Cl⁻).

The desired compound was prepared using the process of Example 1, whilereplacing the wheat starch with a maltodextrin with DPn=7 (determined byproton NMR) and using N,N-dimethylformamide as the solvent.

A maltodextrin pbly(N,N-dimethylglycyl)ester was obtained (yield: 76%)with a degree of substitution of 0.3 (measured by proton NMR).

After quaternization, purification of the quatemized derivative withmethyl iodide in N,N-dimethylformamide produced the desired maltodextrinbetainate chloride (yield: 85%) with a degree of substitution of 0.3.

EXAMPLE 4

A conditioner was prepared comprising: maltodextrin betainate chloridefrom Example 3 0.5 g behenyltrimethylammonium chloride 1.5 g mixture(80/20) of cetylstearyl alcohol and 4 g oxyethylenated cetylstearylalcohol (33 oxyethylene moieties) water qsp 100 g

After applying the conditioner to the hair for two minutes then rinsing,the hair was observed to be soft and easy to disentangle.

EXAMPLE 5

A setting lotion was prepared comprising: maltodextrin betainatechloride from Example 3 0.5 gvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl 0.5 g methacrylateterpolymer, 37% solution in ethanol (ADVANTAGE ® HC 37 from ISP)fragrance, preservative qs water qsp 100 g pH 6

After applying the lotion to the hair and drying, it was observed thatthe hair was soft, lively, and readily styled.

1. A process for preparing a compound of formula (I):

in which: R₁, R₂, and R₃, which may be identical or different, arechosen from linear and branched, saturated and unsaturated C₁-C₃₀hydrocarbon radicals optionally interrupted by at least one hetero atomchosen from N, O, and S and/or optionally substituted with at least oneradical chosen from —OH, halogen and C₆-C₂₂ aryl radicals; A is chosenfrom linear and branched, saturated and unsaturated divalent C₁-C₂₂hydrocarbon radicals, optionally interrupted by at least one hetero atomchosen from N, O, and S, and/or optionally substituted with at least onehydroxyl radical; X⁻ is an anion deriving from an acid chosen frommineral and organic acids; and Y is a polysaccharide residue;comprising: reacting a polysaccharide with an N,N-dialkylaminocarboxylicacid of formula (II):

in the presence of at least one reaction activator; and quaternizing theester formed using a quaternization agent.
 2. The process according toclaim 1, wherein the reaction between the polysaccharide and theN,N-dialkylaminocarboxylic acid is carried out in a polar aproticsolvent.
 3. The process according to claim 2, wherein said polar aproticsolvent is chosen from at least one of dimethylsulphoxide (DMSO) anddimethylformamide.
 4. The process according to claim 1, wherein thequaternization agent is chosen from halides and sulphates.
 5. Theprocess according to claim 4, wherein the halides are chosen fromchlorides, iodides and bromides.
 6. The process according to claim 4,wherein the halides are chosen from C₁-C₃₀ alkyl halides.
 7. The processaccording to claim 6, wherein the halides are a methyl iodide (Mel). 8.The process according to claim 4, wherein the sulphates are chosen fromC₁-C₃₀ alkyl sulphates.
 9. The process according to claim 8, wherein thesulphates are a methyl sulphate (Me₂SO₄).
 10. The process according toclaim 1, wherein the quaternization is carried out at a temperatureranging from about 20° C. to about 70° C.
 11. The process according toclaim 10, wherein the quaternization is carried out at a temperatureranging from about 22° C. to about 27° C.
 12. The process according toclaim 1, wherein the N,N-dialkylaminocarboxylic acid is chosen from atleast one of N,N-dimethylglycine (N,N-dimethylaminoacetic acid),N,N-dimethyl-.beta.-aminopropanoic acid,N,N-dimethyl-.gamma.-aminobutanoic acid, N,N-dimethyl-5-aminopentanoicacid, and N,N-dimethylbenzylamine carboxylic acid.
 13. A process forpreparing a compound of formula (I):

in which: R₁, R₂, and R₃, which may be identical or different, arechosen from linear and branched, saturated and unsaturated C₁-C₃₀hydrocarbon radicals optionally interrupted by at least one hetero atomchosen from N, O, and S and/or optionally substituted with at least oneradical chosen from —OH, halogen and C₆-C₂₂ aryl radicals; A is chosenfrom linear and branched, saturated and unsaturated divalent C₁-C₂₂hydrocarbon radicals, optionally interrupted by at least one hetero atomchosen from N, O, and S, and/or optionally substituted with at least onehydroxyl radical; X⁻ is an anion deriving from an acid chosen frommineral and organic acids; and Y is a polysaccharide residue;comprising: reacting a polysaccharide with a salt of anN,N,N-trialkylammoniocarboxylic acid of formula (III):

wherein the reaction is carried out in a polar aprotic solvent; and thereaction takes place in the presence of at least one reaction activator.14. The process according to claim 13, wherein the polar aprotic solventis chosen from at least one of dimethylsulphoxide (DMSO) anddimethylformamide.
 15. The process according to claim 13, wherein saidsalt of an N,N,N-trialkylammoniocarboxylic acid is chosen from at leastone of salts of N,N,N-trimethylammonioacetic acid,N,N,N-trimethyl-.beta.-ammoniopropa-noic acid,N,N,N-trimethyl-.gamma.-ammoniobutanoic acid,N,N,N-trimethyl-5-ammoniopentanoic acid, andN,N,N-trimethyl-benzylammoni-ocarboxylic acid.
 16. The process accordingto claim 13, wherein said salt is chosen from citrates, lactates,tartrates, halides, and sulphates.
 17. The process according to claim16, wherein said halides are chosen from chlorides, bromides, andiodides.
 18. The process according to claim 13, wherein said at leastone reaction activator is chosen from carbodiimides,hydroxybenzotriazole, and 4-dimethylaminopyridine.
 19. The processaccording to claim 18, wherein the carbodiimides are aN,N′-diisopropylcarbodiimide. 20-67. (canceled)
 68. The processaccording to claim 1, wherein said at least one reaction activator ischosen from carbodiimides, hydroxybenzotriazole, and4-dimethylaminopyridine.
 69. The process according to claim 68, whereinthe carbodiimides are a N,N′-diisopropylcarbodiimide.